Fast simultaneous determination of traces of Cu(II) and Co(II) in soils and sediments with the luminol/perborate chemiluminescent system

A flow injection analysis method based on ion chromatography and luminol chemiluminescence detection was used for the simultaneous determination of copper (II) and cobalt (II) trace levels in soils and sediments following microwave-assisted acid digestion. Detection was based on chemiluminescence (CL) of the luminol–perborate system in an alkaline medium, which is catalyzed by both transition metals. The concentration and pH of the eluent (oxalic acid) was found to affect CL intensities and retention times, both of which were inversely proportional to the oxalic acid concentration. The calibration curves for both metal ions were linear and allowed a limit of detection of 0.003 μg l^?1 for cobalt (II) and 0.014 μg l^?1 for cooper (II) to be calculated. The proposed method was successfully used to determine both metal ions in certified reference materials of stream and river sediments and soil samples. Based on the results, the determination is free of interferences from the usual concomitant ions.     

Mineralization of integrated gasification combined-cycle power-station wastewater effluent by a photo-fenton process

The aim of this work was to study the mineralization of wastewater effluent from an integrated-gasification combined-cycle (IGCC) power station sited in Spain to meet the requirements of future environmental legislation. This study was done in a pilot plant using a homogeneous photo-Fenton oxidation process with continuous addition of H₂O₂ and air to the system.The mineralization process was found to follow pseudo-first-order kinetics. Experimental kinetic constants were fitted using neural networks (NNs). The NNs model reproduced the experimental data to within a 90% confidence level and allowed the simulation of the process for any values of the parameters within the experimental range studied. At the optimum conditions (H₂O₂ flow rate = 120 mL/h, [Fe(II)] = 7.6 mg/L, pH = 3.75 and air flow rate = 1 m³/h), a 90% mineralization was achieved in 150 min.Determination of the hydrogen peroxide consumed and remaining in the water revealed that 1.2 mol of H₂O₂ was consumed per each mol of total organic carbon removed from solution. This result confirmed that an excess of dissolved H₂O₂ was needed to achieve high mineralization rates, so continuous addition of peroxide is recommended for industrial application of this process.Air flow slightly improved the mineralization rate due to the formation of peroxo-organic radicals which enhanced the oxidation process.     

Variation and persistence of the middle rocky intertidal community of central Chile,with and without human harvesting

Humans are an important intertidal predator in central Chile. Following a five-year study we report on the effects of the exclusion of humans from the rocky intertidal at Las Cruces, central Chile. The middle intertidal of harvested and non-harvested areas diverged in species diversity and composition during the experiment. In harvested areas the middle intertidal rocky shore was dominated throughout the study by a monoculture of mussels, Perumytilus purpuratus. When humans were excluded, the middle intertidal community switched to one dominated by barnacles (predominantly Jehlius cirratus and Chthamalus scabrosus); this community has persisted for at least three years, despite the presence of forces e.g. mussel larvae, that have the potential to alter the community structure. Such changes were mediated by the muricid gastropod Concholepas concholepas, a key-stone predator. As a consequence of the above changes, the species diversity, H', (primary space occupiers) in the non-harvested area increased from H'=0 at the beginning of the study in 1983 (when the middle intertidal community was dominated by mussels), to values ca H'=2 toward the middle of the study in 1984 (which coincided with the maximum predatory impact of C. concholepas) and subsequently decreasing to ca H'=0.5 at the end of the study in 1987 (when the middle intertida community was dominated by barnacles).Please address all correspondence to J. C. Castilla, Department of Zoology, University of Washington, Seattle, Washington 98195, USA, until March 1990     

Photo-Fenton-assisted ozonation of p-Coumaric acid in aqueous solution

The degradation of p-Coumaric acid present in olive oil mill wastewater was investigated as a pretreatment stage to obtain more easily biodegradable molecules, with lower toxicity that facilitates subsequent anaerobic digestion. Thus, photo-Fenton-assisted ozonation has been studied and compared with ozonation at alkaline pH and conventional single ultraviolet (UV) and acid ozonation treatments. In the combined process, the overall kinetic rate constant was split into various components: direct oxidation by UV light, direct oxidation by ozone and oxidation by hydroxyl radicals. Molecular and/or radical ozone reaction was studied by conducting the reaction in the presence and absence of tert-butylalcohol at pHs 2, 7 and 9. Ozone oxidation rate increases with pH or by the addition of Fenton reagent and/or UV radiation due to generation of hydroxyl radicals, *OH. Hydrogen peroxide and ferrous ion play a double role during oxidation since at low concentrations they act as initiators of hydroxyl radicals but at high concentrations they act as radical scavengers. Finally, the additional levels of degradation by formation of hydroxyl radicals have been quantified in comparison to the conventional single processes and an equation is proposed for the reaction rate as a function of studied operating variables.     

Semiconductor-assisted photocatalytic degradation of reactive dyes in aqueous solution

This work reports the semiconductor-assisted photochemical degradation of reactive dyes. In an oxygenated-UV-ZnO system almost total decolorization of Remazol Brilliant Blue R, Remazol Black B, Reactive Blue 221 and Reactive Blue 222 was observed in reaction times of about 60 min. Extending the photochemical treatment up to 120 min, mineralization higher than 80% for all the dyes was observed. During the same period, the residual acute toxicity was significantly reduced only for Remazol Black B. A systematic optimization study carried out by factorial design showed that for the reactive dyes tested, the ZnO semiconductor exhibits a better efficiency than that observed with anatase TiO2. A synergistic effect in the coupled TiO2-ZnO system was not observed.     

Arsenic and sulfur nanoparticle synthesis mimicking environmental conditions of submarine shallow-water hydrothermal vents

Arsenic and sulfur mineralization is a natural phenomenon occurring in hydrothermal systems where parameters like temperature and organic matter(OM) can influence the mobilization of the toxic metalloid in marine environments. In the present study we analyze the influence of temperature and OM(particularly sulfur-containing additives) on As and S precipitation based on the recent discovery of As-rich nanoparticles in the hydrothermal system near the coast of the Greek island Milos. To this end, ...     

Transmission distance of chemical cues from coral habitats: implications for marine larval settlement in context of reef degradation

The present study (Ishigaki Island, Japan) explored the distance of transmission of chemical cues emitted by live versus dead coral reefs (Exp. 1: High performance liquid chromatography (HPLC) analyses with water sampling station at 0, 1, and 2 km away from the reef) and the potential attraction of these chemical cues by larval fish, crustaceans, and cephalopods (Exp. 2: choice flume experiment conducted on 54 Chromis viridis larvae, 52 Palaemonidae sp larvae, and 16 Sepia latimanus larvae). In the experiment 1, HPLC analyses highlighted that the live coral reef (and not the dead coral reef) produced different and distinct molecules, and some of these molecules could be transported to a distance of at least 2 km from the reef with a reduction of concentration by 14–17-fold. In the experiment 2, C. viridis, Palaemonidae sp, and S. latimanus larvae were significantly attracted by chemical cues from a live coral reef (sampling station: 0 km), but not from a dead coral reef. However, only C. viridis larvae detected the chemical cues until 1 km away from the live coral reef. Overall, our study showed that chemical cues emitted by a live coral reef were transported farthest away in the ocean (at least 2 km) compared to those from a dead coral reef and that fish larvae could detect these cues until 1 km. These results support the assumption of a larval settlement ineffective in degraded coral reefs, which will assist conservationists and reef managers concerned with maintaining biodiversity on reefs that are becoming increasingly degraded.     

An individual-based model to study the reproduction of egg bearing copepods: Application to Eurytemora affinis (Copepoda Calanoida) from the Seine estuary,France

Limited empirical studies have elucidated the daily egg production and associated reproductive processes of egg bearing copepod. Herein, we present an individual-based model which constitutes a realistic representation of the reproduction in egg bearing copepods. The model has been parameterized using an extensive set of experimental data obtained from the literature and from the laboratory and field experiments on the estuarine copepod Eurytemora affinis. The proposed model takes into account the adult female longevity, the clutch size and interclutch duration, which is a function of egg maturation time and latency time required by the female after egg hatching to produce a new clutch. The embryonic development time and hatching success are also taken into account. The effect of temperature on the means and variances of above-mentioned reproductive parameters has been also incorporated. A multi agent system based generic platform “Mobidyc” has been used to generate and calibrate the model. The model demonstrates the reproductive parameters of females of E. affinis which is validated through individual based experiments. Temperature specific simulations provide a dynamical explanation of temperature effect on the cumulative egg production. The daily survival principally affects the number of clutches produced per female during its life span. The results obtained in the present study by combining temperature and survival effects reveal the relatively greater importance of the first factor on the daily egg production of egg-carrying copepods. The present model is generic and hence easily applicable to other animals with comparable reproductive strategy.     

Evaluation of boron removal from water by hydrotalcite-like compounds

Layered double hydroxides (LDHs) or hydrotalcite (HT)-like compounds with different kinds of metal ions (Mg-Al and Mg-Fe) in the brucite-like sheets were prepared and their adsorption properties were studied in the boron removal from aqueous solution under laboratory conditions. The hydrotalcites were synthesized by the coprecipitation method and were characterized by chemical analyses, X-ray diffraction (XRD), Fourier Transform infrared spectroscopy (FTIR) and specific surface area measurements (BET). The affinity of these materials with a mixture of B(OH)(3) and B(OH)(4)(-) was studied as a function of contact time, initial pH of the solutions, HT quantity and B concentration (adsorption isotherms). It was found that 120 min is enough time for the equilibrium state to be reached in boron adsorption. Boron removal was independent of the initial pH of the solutions because of the high buffering capacity of the LDHs. On the other hand, the adsorption capacity increases with increasing the adsorbent quantity. The adsorption isotherms, described by the Langmuir model, are of L-type, suggesting that B(OH)(4)(-) is adsorbed preferentially on HT-like materials. Besides, Mg-Al hydrotalcites showed higher adsorption capacity than Mg-Fe. We proposed that in Mg-Al hydrotalcites, the boron removal occurs by both adsorption on external surface and ion exchange, whereas for Mg-Fe it occurs only by surface adsorption. After treatment of a solution containing 5.2 mgBl(-1) with Mg-Al hydrotalcites the final boron concentration reached the recommended limit by WHO for drinking water (0.5 mgl(-1)).     

Simulation of atmospheric PAH emissions from diesel engines

Simulation of atmospheric PAH emissions in a typical European passenger car diesel engine at steady conditions or under a certification cycle is made using in-house software. It is based on neural fitting of experimental data from eight different fuels tested under five operating steady conditions (reproducing modes of the European transient urban/extraurban certification cycle). The software allows the determination of PAH emissions as a function of the fuel composition parameters (aromatic content, cetane index, gross heat power, nitrogen and sulphur content) and operation conditions (torque and engine speed). The mathematical model reproduces experimental data with a maximum error of 20%. This tool is very useful, since changes in parameters can be made without experimental cost and the trend in modifications in PAH emissions is immediately obvious.